U.S. Pat. No. 3,081,519 (Blades et al.) describes a flash-spinning process for producing plexifilamentary film-fibril strands from fiber-forming polymers. A solution of the polymer in a liquid, which is a non-solvent for the polymer at or below its normal boiling point, is extruded at a temperature above the normal boiling point of the liquid and at autogenous or higher pressure into a medium of lower temperature and substantially lower pressure. This flash-spinning causes the liquid to vaporize and thereby cool the exudate which forms a plexifilamentary film-fibril strand of the polymer. Preferred polymers include crystalline polyhydrocarbons such as polyethylene and polypropylene.
According to Blades et al. in both U.S. Pat. No. 3,081,519 and U.S. Pat. No. 3,227,784, a suitable liquid for the flash spinning desirably (a) has a boiling point that is at least 25.degree. C. below the melting point of the polymer; (b) is substantially unreactive with the polymer at the extrusion temperature; (c) should be a solvent for the polymer under the pressure and temperature set forth in the patent (i.e., these extrusion temperatures and pressures are respectively in the ranges of 165 to 225.degree. C and 545 to 1490 psia); (d) should dissolve less than 1% of the polymer at or below its normal boiling point; and should form a solution that will undergo rapid phase separation upon extrusion to form a polymer phase that contains insufficient solvent to plasticize the polymer. Depending on the particular polymer employed, the following liquids are useful in the flash-spinning process: aromatic hydrocarbons such as benzene, toluene, etc.; aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, and their isomers and homologs; alicyclic hydrocarbons such as cyclohexane; unsaturated hydrocarbon's; halogenated hydrocarbons such as trichlorofluoromethane, methylene chloride, carbon tetrachloride, chloroform, ethyl chloride, methyl chloride; alcohols; esters; ethers; ketones; nitriles; amides; fluorocarbons; sulfur dioxide; carbon disulfide; nitromethane; water; and mixtures of the above liquids. The patents illustrate certain principles helpful in establishing optimum spinning conditions to obtain plexifilamentary strands. Blades et al. state that the flash-spinning solution additionally may contain a dissolved gas, such as nitrogen, carbon dioxide, helium, hydrogen, methane, propane, butane, ethylene, propylene, butene, etc to assist nucleation by increasing the "internal pressure" and lowering the surface tension of the solution. Preferred for improving plexifilamentary fibrillation are the less soluble gases, i.e., those that are dissolved to a less than 7% concentration in the polymer solution under the spinning conditions. Common additives, such as antioxidants, UV stabilizers, dyes, pigments and the like also can be added to the solution prior to extrusion.
U.S. Pat. No. 3,227,794 (Anderson et al.) discloses a diagram similar to that of Blades et al. for selecting conditions for spinning plexifilamentary strands. A graph is presented of spinning temperature versus cloud-point pressure for solutions of 10 to 16 weight percent of linear polyethylene in trichlorofluoromethane. Anderson et al. describe in detail the preparation of a solution of 14 weight percent high density linear polyethylene in trichlorofluoromethane at a temperature of about 185.degree. C. and a pressure of about 1640 psig which is then flash-spun from a let-down chamber at a spin temperature of 185.degree. C. and a spin pressure of 1050 psig. Very similar temperatures, pressures and concentrations have been employed in commercial flash-spinning of polyethylene into plexifilamentary film-fibril strands, which were then converted into sheet structures.
Although trichlorofluoromethane has been a very useful solvent for flash-spinning plexifilamentary film-fibril strands of polyethylene, and has been the dominant solvent used in commercial manufacture of polyethylene plexifilamentary strands, the escape of such a halocarbon into the atmosphere has been implicated as a source of depletion of the earth's ozone layer. A general discussion of the ozone-depletion problem is presented, for example, by P. S. Zurer, "Search Intensifies for Alternatives to Ozone-Depleting Halocarbons", Chemical & Engineering News, pages 17-20 (Feb. 8, 1988).
Clearly, what is needed is a flash-spinning process which uses a spin liquid which does not have the deficiencies inherent in the prior art. It is therefore an object of this invention to provide an improved process for flash-spinning plexifilamentary film-fibril strands of a fiber-forming polyolefin, wherein the spin liquid used for flash-spinning is not a depletion hazard to the earth's ozone layer. It is also an object of this invention to provide an improved process for flash-spinning plexifilamentary film-fibril strands of fiber-forming polyolefin, wherein the resulting flashspun plexifilaments have increased tenacity and improved fibrillation. Others objects and advantages of the present invention will become apparent to those skilled in the art upon reference to the detailed description of the invention which hereinafter follows.